EP3131942A1 - Poly(beta-methyl-delta-valerolactone) block polymers - Google Patents
Poly(beta-methyl-delta-valerolactone) block polymersInfo
- Publication number
- EP3131942A1 EP3131942A1 EP15719127.1A EP15719127A EP3131942A1 EP 3131942 A1 EP3131942 A1 EP 3131942A1 EP 15719127 A EP15719127 A EP 15719127A EP 3131942 A1 EP3131942 A1 EP 3131942A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pmvl
- block
- polymer
- plla
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 title claims description 88
- -1 Poly(beta-methyl-delta-valerolactone) Polymers 0.000 title claims description 26
- 229920001400 block copolymer Polymers 0.000 claims abstract description 53
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 54
- 239000004626 polylactic acid Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 37
- 230000009477 glass transition Effects 0.000 claims description 24
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- 238000005859 coupling reaction Methods 0.000 claims description 18
- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 8
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- 229920002961 polybutylene succinate Polymers 0.000 claims description 7
- 239000004631 polybutylene succinate Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 5
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
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- 238000006116 polymerization reaction Methods 0.000 description 39
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- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 3
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- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical compound NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007155 step growth polymerization reaction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920006250 telechelic polymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YNPXMOHUBANPJB-UHFFFAOYSA-N zinc;butan-1-olate Chemical compound [Zn+2].CCCC[O-].CCCC[O-] YNPXMOHUBANPJB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4275—Valcrolactone and/or substituted valcrolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
Definitions
- This disclosure relates to, among other things, block copolymers having at least one poly(P-methyl-5-valerolactone) block.
- this disclosure describes the use of controlled polymerization techniques to produce well defined polymers having poly(P-methyl-5-valerolactone) (PMVL) blocks.
- the PMVL blocks can be formed from biosynthesized P-methyl-5- valerolactone (MVL).
- the elastomeric polymer PMVL is combined with hard polymers to produce block copolymers having soft (PMVL) and hard blocks.
- hard block-PMVL-hard block triblock polymers are described herein.
- hard blocks are semicrystalline poly(L-lactide) or glassy poly(lactide) (PLLA or PLA, respectively) blocks or polyurethane blocks.
- PMVL block copolymers A variety of methods for producing PMVL block copolymers are described herein. Such methods include polymerizing monomers from a living PMVL polymer or a telechelic PMVL block and coupling a PMVL block to another polymer block.
- One or more embodiments of the compounds, polymers, compositions or methods described herein may provide one or more advantages relative to existing compounds, polymers, compositions or methods.
- block copolymers in various embodiments described herein, having one or more blocks formed from biosynthesized monomers have mechanical properties akin to commercially available thermoplastics and elastomers.
- the reaction parameters to produce such block copolymers can be readily changed to tune the mechanical properties of the resulting block copolymer.
- FIG. 1 Polymerization of PM5VL leading to PMVL and chain extension with ( ⁇ )- or (-)- lactide (LA or LLA) yielding P(L)LA-PMVL-P(L)LA triblock polymer.
- TBD represents triazabicyclodecene and HO-R-OH represents 1,4-phenylenedimethanol.
- FIG. 2 Conversion over time for bulk polymerization of M5L using TBD as a catalyst and psuedo-first-order kinetics plot for same kinetics data.
- FIG. 3 Thermodynamics of MVL bulk polymerization line shows linear best fit used to determine ⁇ ⁇ ° and AS P ° for the bulk polymerization (-13.8 +0.3 kJ mol "1 and -46+1 J mol "1 K “1 , respectively).
- FIG. 4. (a) Overlay of size exclusion chromatography traces obtained from PMVL (20.0 kg mol “1 ) and a corresponding PLLA-PMVL-PLLA (9.1-20.0-9.1 kg mol "1 ) triblock polymer, (b) 13 C NMR spectra obtained from (bottom) PMVL, (middle) PLLA (10.0 kg mol "1 ), and (top) PLLA-PMVL-PLLA (9.1-20.0-9.1 kg mol "1 ).
- FIG. 6 shows a synthesis scheme of (PLLA-PMVL) n and (PLA-PpM5VL) n Multiblocks using a diacid chloride coupling approach
- FIG. 7 shows a representative example of size-exclusion chromatograms for a telechelic
- MVL MVL
- PLA-PMVL-PLA PLA-PMVL-PLA
- corresponding (PMVL-PLA) n multiblock prepared using diacid chloride coupling approach.
- FIG. 8 shows a synthesis scheme of (PLLA-PMVL) n and (PLA-PpM5VL) n Multiblocks using an isocyanate coupling approach
- FIG. 9 shows a representative example of size-exclusion chromatograms for a telechelic
- FIG. 10 shows a representative examples of room temperature uniaxial extension of
- FIG. 11 shows PLLA-PMVL-PLLA/PDLA-PMVL-PDLA sterocomplexes.
- FIGS. 12A-B show DSC thermograms for PLLA-PMVL-PLLA (A) and sc-PMVL-Psc
- FIGS. 13A-B show DMA isochronal temperature ramps for PLLA-PMVL-PLLA (A)
- FIG. 14 shows representative examples of room temperature uniaxial extension of PLLA- PMVL-PLLA, sc-PMVL-sc, and PLA-PMVL-PLA triblock elastomers. Experiments were conducted with constant crosshead velocity of 50 mm min "1 .
- FIG. 15 shows synthesis of PpM5VL polyurethanes using methylene diphenyl diisocyanate
- FIG. 17 shows representative tensile data for a PMVL polyurethane PM VL-PMDM2230
- FIG. 18 shows representative data for hysteresis test of PMVL polyurethane PMVL- PMDM2230 (0.4). The test is for 20 cycles of loading and unloading with crosshead
- a PMVL block can be formed from biosynthesized MVL.
- a "biosynthesized compound” is a compound in which at least one step of its synthesis is performed by an organism, such as a microbe.
- a biosynthesized compound can be distinguished from a similar compound produced by conventional chemical processes from, for example, a petroleum-based material by the ratio of 14 C to 12 C in a sample of the compound.
- a sample of the compound that is biosynthesized will possess a measurable amount of 14 C isotopes incorporated into the compound molecules.
- a sample of the compound prepared from petroleum-based materials will possess negligible levels of 14 C.
- a sample or composition that includes a biosynthesized compound will typically possess a 14 C/ 12 C ratio greater than zero.
- a sample or composition that includes a biosynthesized compound can have a CI C ratio greater than 0.25x 10 such as, for example, a CI C ratio from 0.25 10 12 to 1.2x l0 ⁇ 12 .
- the PMVL block of a block copolymer described herein has a
- the PMVL block can have a 14 C/ 12 C ratio greater than or equal to 0.25 ⁇ 10 such as, for example, a CI C ratio from 0.25 x 10 to 1.2x l0 ⁇ 12 .
- a block copolymer described herein has a 14 C/ 12 C ratio greater than zero.
- the block copolymer can have a 14 C/ 12 C ratio greater than 0.25 ⁇ 10 12 such as, for example, a 14 C/ 12 C ratio from 0.25x l0 ⁇ 12 to 1.2x l0 ⁇ 12 .
- Block copolymers allow for the properties of different polymer materials to be extended by combining two or more different polymers in a final product.
- the properties of a block copolymer can be tailored by tuning the length and the type of blocks used.
- a block copolymer including a PMVL block can be a di-block copolymer (A-B), a tri-block copolymer (e.g., A-B-C, A-B-A or B-A-B), or a multiblock copolymer [e.g., (A-B) n ].
- the second block has a glass transition temperature greater than the PMVL block.
- the second block can have a glass transition temperature greater that the glass transition temperature of the PMVL block by about 10 °C or more, by about 20 °C, by about 30 °C or more, about 40 °C or more, about 50 °C or more, about 60 °C or more, or about 70 °C or more.
- a second block will have a glass transition temperature no more than about 300 °C greater than a PMVL block.
- the PMVL block can have any suitable glass transition temperature.
- the PMVL block has a Tg of less than -30 °C.
- the PMVL block can have a Tg of less than -40 °C or less than -50 °C.
- the PMVL block has a Tg greater than -100 °C.
- the PMVL block has a Tg of about -51 °C.
- the block copolymers described herein can include a PMVL soft block and a hard block.
- a hard block has a glass transition temperature of about room temperature or greater.
- the hard block has a glass transition temperature of about 25 °C or greater, such as in a range from about 30 °C to about 90 °C, in a range from about 40 °C to about 80 °C, or in a range from about 50 °C to about 70 °C.
- polylactic acid which can be a hard block can have a glass transition temperature in a range from about 60 °C to about 65 °C.
- hard blocks are crystalline or semicrystalline blocks at room temperature (e.g., at about 23 °C).
- hard blocks include polylactic acid blocks, polycaprolactone blocks, polygylcolide blocks, polytrimethylene carbonate blocks, polyhydroxybutyrate blocks, polybutylene succinate blocks, polyurethane blocks, or copolymers of these blocks, and the like.
- the hard block can be a biobased block such as a biosynthesized polylactic acid block, a biosynthesized polyhydroxybutyrate block, or a biosynthesized polybutylene succinate block.
- the PMVL (soft) segments can influence the elastic nature of the block copolymer and can contribute to low temperature properties and extensibility of the block copolymer.
- the block copolymers described herein are thermoplastic elastomers that combine a PMVL elastomer with a hard block thermoplastic polymer.
- thermoplastic elastomers behave like elastomers at temperatures between the glass transition temperatures of PMVL and the polymer of the hard block and can be processed like thermoplastics at temperatures above the glass transition temperature of the polymer of the hard block.
- thermoplastic polymers examples include those hard block polymers listed above, such as polylactic acid, polycaprolactone, polygylcolide, polytrimethylene carbonate, polyhydroxybutyrate, polybutylene succinate, polyurethane, polystyrene, polyolefm such as polyethylene or polypropylene, or copolymers of these polymers, and the like.
- the thermoplastic polymers used as hard blocks can be a biobased block such as biosynthesized polylactic acid, biosynthesized polyhydroxybutyrate, or biosynthesized polybutylene succinate.
- PMVL blocks may be formed in any suitable manner.
- PMVL may be formed via ring-opening transesterification polymerization (ROTEP) of MVL employing an appropriate initiator and catalyst.
- ROTEP ring-opening transesterification polymerization
- Any suitable catalyst may be employed.
- suitable catalysts include metal catalysts or organocatalysts, such as tin octoate; triethyl aluminum; zinc dibutoxide; titanium tetrabutoxide; triazobicyclodecene (TBD); 1,4- Benzene dimethanol (BDM); diphenyl phosphate (DPP); and the like.
- the initiator may be an organometal (e.g. alkyl lithium, alkyl magnesium bromide, alkyl aluminum, etc.), a metal amide, an alkoxide, a phosphine, an amine, an alcohol, or the like.
- the initiator is an alcohol.
- the initiator may be monofunctional or multi-functional.
- suitable ring opening polymerization initiators include benzyl alcohol; 1,4 benzene dimethanol; and the like.
- One of skill in the art will understand that the ratio of monomer to initiator may be varied to obtain polymers of different molecular weights.
- Polymerization of MVL may occur in solution, in the melt, or as a suspension.
- the PMVL blocks can be of any suitable length.
- a PMVL block has a mass average molar mass (M w ) of 0.25 kDa or greater, such as 0.5 kDa or greater, or 1 kDa or greater.
- M w mass average molar mass
- a PMVL block has M w of from about 1 to about 500 kDa, such as from about 2 to about 250 kDa or from about 3 to about 100 kDa.
- Non-PMVL blocks can be formed in any suitable manner, such as polymerization of one or more monomers, or the like.
- polylactic acid may be formed via ring opening polymerization of lactide or by condensation of lactic acid.
- the polylactic acid blocks are formed via ring opening polymerization of lactide.
- Any suitable catalyst may be employed for ring opening polymerization of lactide. Examples of suitable catalysts and initiators include those catalysts and initiators described above with regard to polymerization of MVL. Polymerization of lactide may occur in solution, in the melt or as a suspension.
- polyhydroxybutyrate may be formed via polymerization of hydroxybutyryl-CoA.
- polyhydroxybutyrate may be isolated from a microorganism, such as Ralstonia eutrophus or Bacillus megaterium, and modified for conjugation to a PMVL block. Ring-opening polymerization of beta butyrolactones or copolymerization of epoxides and carbon monoxide represent chemical routes to polyhrdroxybutyrates .
- polybutylene succinate may be formed via esterification of succinic acid with 1 ,4 butanediol to form polybutylene succinate oligomers which can then be transesterified to form larger molecular weight polymers.
- Any suitable catalyst may be used for either step.
- a titanium, zirconium, tin or germanium-based catalyst may be used for the transesterification reaction.
- polyurethane may be formed via reaction of a di- or polyisocyanate with a polyol to achieve a polyurethane.
- the polyurethane is a hard block containing phase-separated and semi-crystalline domains.
- Any suitable compound having two or more isocyanate groups and any suitable polyol can be used to form a polyurethane.
- suitable compounds having two or more isocyanate groups include methylene diphenyl diisocyanate, isophorone diisocyanate, L- lysine diisocyanate, and the like.
- suitable polyols include 1,3 propane diol, 1,4 butane diol, and the like.
- Non-PMVL blocks such as hard blocks, can be of any suitable length.
- a non-PMVL block e.g., an individual end block
- M w mass average molar mass
- a block will have a Mw of about 0.25 kDa or greater.
- Block copolymers described herein can be formed in any suitable manner.
- non-PMVL blocks are added to PMVL blocks (or non- PMVL blocks) via living polymerization.
- monomers forming a non-PMVL block can be added to a living PMVL (or non-PMVL), preferably at equilibrium.
- the catalyst employed for the polymerization of the living polymer is suitable for use in polymerizing the later added monomers for forming the other block or blocks.
- one or more additional catalysts may be added as appropriate.
- an ABA triblock copolymer is formed via living polymerization.
- Monomers for forming the B block can be polymerized and monomers forming the A blocks can be added to the living B block polymer.
- o,L-Lactide, D- Lactide or L-Lactide can be added to a living PMVL.
- triazobicyclodecene (TBD) can be used to catalyze the MVL polymerization and polymerization of the lactide (e.g., via ring opening polymerization).
- non-MVL monomers are added to a previously-purified telechelic PMVL (or telechelic poly(non-MVL)).
- the purified telechelic PMVL (or telechelic poly(non-MVL)) and non-MVL monomer (or MVL) can be combined in solution or in melt/bulk and a catalyst can be added to cause polymerization of the non-MVL monomer (or MVL) from one or more ends of the previously-purified telechelic PMVL (or telechelic poly(non-MVL)).
- the amount of added non-MVL monomer (or MVL) added can depend on the target composition of the block polymer.
- an ABA block copolymer is formed by adding non-MVL monomers and a catalyst to a telechelic PMVL in solution or in melt/bulk to cause polymerization of the non-MVL monomer from the ends of the previously-purified telechelic PMVL.
- non-PMVL oligomers such as hard block oligomers, are reacted with telechelic PMVL to form a copolymer.
- PMVL-(non-PMVL) coblocks can be synthesized to form multiblocks.
- Coupling agents such as those generally known in the art, can be used to couple the oligomers to form a block copolymer or to couple the coblocks to form the multiblocks.
- multiblocks can be synthesized conveniently from dihydroxy telechelic PLA-PMVL-PLA triblock using a coupling approch.
- Coupling agents that can be used for this purpose include diacid chlorides, such as for example terephthalic acid and sebacoyl chloride, diisocyantes, such as for example methylene diisocyante, and divinyl adipate.
- a block copolymer described herein may include any suitable amount of PMVL and non- PMVL block polymer.
- the weight percent of hard block polymer in a hard block-PMVL block copolymer can be from about 5% to about 95%, such as froml0% to about 90%, from about 20%) to about 70%>, or from about 25% to about 60%>.
- non-PMVL block polymer and PMVL may be modified to achieve desired properties of a block copolymer (e.g., a PLA-PMVL-PLA ABA block copolymer).
- Hard blocks tend to be hard, while PMVL tends to be soft.
- the properties of the resulting copolymer can be tuned as desired. For example, incorporation of relatively small amounts of the hard block polymer, soft highly elastic polymeric material may result. By way of further example, incorporation of higher amounts of the hard block polymer, stiffer and ductile plastics may result.
- a block copolymer described herein has an elastic modulus of from about 0.1 MPa to about 2500 MPa, such as from about 0.2 MPa to about 1500 MPA, from about 0.5 MPa to about 500 MPa, from about 1 MPA to about 400 MPa, or from about 1.5 MPa to about 300 MPa.
- block copolymer described herein has a percent elongation of from about 5% to about 5000%), such as from about 10%> to about 4500%), from about 100% to about 4000%, from about 200% to about 3000%, or from about 300% to about 2000%.
- polylactide and “polylactic acid” are used interchangeably.
- a polylactide can be formed from o-lactide, L-lactide or D,L-lactide, or combinations thereof.
- EXAMPLE 1 PMVL and PLA-PMVL-PLA block copolymers
- Materials and Methods Biosynthesis of MVL: MVL was synthesized generally as described in Example 2 of WO2014/172596A2, entitled BIOSYNTHETIC PATHWAYS AND PRODUCTS, published on 23 October 2014.
- Benzyl alcohol (99%), Sigma-Aldrich) was purchased and used without additional purification.
- d ,L- Lactide was a kind gift from Ortec Incorporated and was used as received.
- L -Lactide was a kind gift from Natureworks and was recrystallized twice from dry toluene and dried prior to use.
- Toluene and dichloromethane (DCM) was passed through a home -built solvent purification system, which includes a column of activated alumina and a column of molecular sieves operated under a positive pressure of nitrogen gas.
- Anhydrous methanol (Sigma-Aldrich) and chlorform (Fisher) were purchased and used as received.
- Triethylamine 99.5%>, Macron
- benzoic acid 99.5%>, Fisher
- PMVL To synthesize PMVL a mono functional (benzyl alcohol) or difunctional (1,4 benzene dimethanol) alcohol was added to monomer in a pressure vessel or glass vial and stirred with a magnetic stir bar until completely dissolved. The ratio of monomer to alcohol was varied to target polymers of different molecular weights. When the initiator was dissolved an appropriate amount of catalyst (-0.05-0.2 mol% TBD or -0.5 mol% DPP) relative to monomer was added to initiate the polymerization. The reaction was stirred and the conversion monitored using 1H NMR of crude quenched aliquots dissolved in CDCI 3 .
- the reaction was quenched by the addition of 5 equivalents, relative to catalyst, of either 1M benzoic acid in chloroform (TBD catalyzed reactions) or triethylamine (DPP catalyzed reactions).
- TBD catalyzed reactions 1M benzoic acid in chloroform
- DPP catalyzed reactions triethylamine
- poly((L)LA)-£-PMVL-£-poly((L)LA) Addition of lactide to living polymerization: To prepare poly((L)LA)-£-PMVL-£-poly((L)LA) a solution of D ,L-Lactide or L -Lactide in DCM (1M) was added slowly to a living TBD catalyzed polymerization at equilibrium while stirring manually with a glass stir rod. The amount of lactide solution added depended on the target composition of the block polymer. To obtain purified polymers the samples were quenced with benzoic acid, diluted with chloroform, precipiated in methanol, and dried.
- DPP is not capable of catalyzing the polymerization of lactide therefore addition D,L- Lactide in DCM PMVL in the presence of this catalyst resulted in depolymerization of PMVL rather than the synthesis of a block polymer.
- poly((L)LA)-3 ⁇ 4-PMVL-3 ⁇ 4-poly((L)LA):7SD catalyzed addition of lactide to purified telechelic PMVL in solution To prepare poly((L)LA)-£-PMVL-£-poly((L)LA) from a previously isolated and purified PMVL using TBD the prepolymer was dissolved in a 1 M solution of D ,L-Lactide or L -Lactide in DCM, when fully dissolved 0.1 mol% TBD (relative to lactide) was added. The solution was stirred for 10 minutes, then quenched via the addition 5 equivalents of benzoic acid relative to TBD. To obtain purified polymers the samples were diluted with chloroform, precipiated in methanol, and dried.
- poly((L)LA)-3 ⁇ 4-PMVL-3 ⁇ 4-poly((L)LA) Sn(oct)2 catalyzed addition of lactide to purified telechelic PMVL in melt/bulk: To prepare poly((L)LA)-6-PMVL-6-poly((L)LA) from a previously isolated and purified PMVL in the melt the prepolymer was added to an appropriate amount of o,L-Lactide or L-Lactide in a 5 -necked kettle reactor fitted with an overhead stir assembly, thermometer, gas inlet, bubbler, and septum. The contents were heated while stirring under constant argon flow until the internal temperature reached 180 °C.
- the relative mass average molar mass (M m _ P s) of unpurified polymer samples was determined via size exclusion chromatography (SEC) on a liquid chromatograph (Agilent 1100 series) equipped with a HP 1047A RI detector. Polymer samples were prepared in chloroform and passed through three successive Varian PLgel Mixed-C columns with chloroform as the mobile phase at 35 °C with a flow rate of 1 mL/min. Molecular weight characteristics of the samples were referenced to polystyrene standards (Polymer Laboratories).
- DSC Differential scanning calorimetry
- Discovery DSC instrument with hermetically sealed T-zero aluminum pans.
- the samples were equilibrated at 150 °C and cooled to -75 °C at 5 °C min 1 followed by heating to 150 °C at the same rate. Glass transition temperatures are reported upon the second heating cycle.
- Thermogravimetric analysis was performed on a Perkin Elmer Diamond TGA/DTA. Samples were heated in aluminum pans under nitrogen atmosphere at a rate of 10 °C min "1 .
- Polymer density was determined using the following method: Glycerol (99%, Riedel-de
- the overall non-natural pathway has three components: (1) overexpression of the mevalonate producing enzymes; (2) introduction of the fungal siderophore proteins to synthesize anhydromevalonolactone (AML); (3) reduction of AML to MVL by enoate reductases.
- the resulting anhydromevalonolactone was isolated by solvent extraction using chloroform and hydrogenated to MVL using Pd/C as the catalyst (bulk, room temperature, 350 psi H 2 , 12 h) at >99% conversion.
- the crude product was subsequently purified by distillation into polymerization-grade monomer.
- dihydroxy terminated PMVL to prepare triblock polymers with poly(lactide) endblocks. This was easily accomplished by adding a solution of ( ⁇ ) or (-)-lactide (LA or LLA) directly to a polymerization of MVL that was near equilibrium.
- P(L)LA-PMVL-P(L)LA triblock polymers readily microphase separate at only moderate molar masses as evidenced by differential scanning calorimetry (DSC) and small angle x-ray scattering (SAXS).
- DSC differential scanning calorimetry
- SAXS small angle x-ray scattering
- PLA-PMVL-PLA from ( ⁇ )-lactide, LA
- PLLA-PMVL-PLLA from (-)-lactide, LLA
- SAXS data from these triblocks showed well-defined scattering peaks that correspond to self-assembled nanostructures with principal spacings ranging from 20 to 50 nm (FIG. 4D, Table 3).
- the mechanical and thermal properties of these ordered block polymers are influenced by molar mass, tacticity of the poly(lactide) segments, and composition.
- the use of semi-crystalline PLLA endblocks leads to remarkably strong elastomers that rival commercially available petroleum based block copolymers in terms of recoverability, tensile strength, and ultimate elongation (FIG. 5 and Table 1).
- This bioderived monomer can be readily converted from the neat state to a rubbery hydroxytelechelic polymer using controlled polymerization techniques at ambient temperature; addition of either ( ⁇ ) or (-)-lactide to a PMVL midblocks leads to well defined ABA triblock polymers.
- ABA triblock polymers We have shown that the thermal and mechanical properties of these materials can be tuned by controlling molar mass, arcitecture, and endblock tacticity and have specifically demonstrated thermoplastic elastomers with properties similar to commercially availible styrenic block polymers. This work lays the foundation for the production of new biobased polymeric materials with a wide range of potential properties and applications.
- composition calculated from the mass average molar mass of the corresponding midblock determined by LS-SEC and the lactide content of the purified triblock determined by 1H NMR.
- b weight percent of lactide in triblock determined using 1H NMR analysis.
- c Volume fraction of (L)LA blocks determined using densities of 1.248 g cm “3 and 1.10 g cm “3 for poly(lactide) and poly(5MVL), respectively.
- Glass transition temperatures and melting points, and enthalpy of fusion were determined using the second DSC heating ramp at a rate of 5 °C min "1 after previously cooling from 200 °C at the same rate.
- e Percent crystallinity for the entire triblock was calculated from the enthalpy of fusion and a reference heat of fusion of 94 J/g for the a- form of crystalline PLLA.
- Order to disorder transition temperatures determined by DMA temperature ramps heating a a rate of 1 °C min "1 with a constant frequency of 1 rad/s and a strain of 1%. Transition temperatures were also determined using variable temperature SAXS (listed in parentheses). For samples 5, 7, and 8 the transition temperature was above the degradation temperature of the sample.
- g Domain spacing calculated from primary SAXS peak at room temperature (20 °C) after heating above the order to disorder transition and annealing in a vacuum oven at 100 °C for a minimum of 12 hours prior to slow cooling to ambient temperature.
- a film was prepared by casting from a solution of chloroform, dried and annealed at 100 °C for 12 hours prior to slow cooling to ambient temperature.
- h Sample is disordered by SAXS. 1 Order to disorder transition not apparent by SAXS or rheology prior to onset of degradation, likely >180 °C.
- PLA-PMVL-PLA and PLLA-PMVL-PLLA triblocks were synthesized via chain extension of dihydroxy telechelic PMVL with ( ⁇ )-lactide or (-)-lactide.
- Two different synthetic methods have been used: 1.) Lactide monomer dissolved in dichloromethane or toluene can be added directly to a living (TBD-catalyzed) PMVL at equilibrium. 2.) Lactide can be added to PMVL in the melt or in toluene using Sn(oct) 2 as a catalyst. There is no evidence of depolymerization or transesterification between the PMVL and PLA blocks when either method is used.
- Multib locks can be synthesized conveniently from dihydroxy telechelic PLA-PMVL- PLA triblock using a coupling approch.
- Coupling agents that have been used sucessfully for this purpose are diacid chlorides (for example terephthalic acid and sebacoyl chloride), diisocyantes (for example methylene diisocyante), and divinyl adipate.
- coupling efficiency as the ratio the molar mass of the multiblock to the molar mass of the parent triblock as determined by size exclusion chromatography.
- Coupling effiencies for the methods described here range from 1.1 to 4.0 depending on polymer molar mass and stiociometry of coupling agent to alcohol groups on the polymer. This efficeincey is basically correlated to the number average degree of polymerization for the multiblock. Most typically the coupling efficiency is about 2.0.
- Procedure 1 One pot synthesis of (PMVL-PLA) n using diacid chloride: In a glovebox with a nitrogen atmosphere 94.4 miligrams of 1,4-benzene dimethanol was added to a pressure vessel contaioning 20.0385 grams MVL. The solution was stirred until the initiator was fully dissolved then 49.1 milligrams of TBD were added. After one hour an alioquat was removed for characterizaiton and ( ⁇ )-lactide (8.3716 g) in toluene (120 ml) was added. The polymerization was stirred for 20 minutes and a second aliquot was removed.
- FIG. 6 shows a synthesis scheme of (PLLA-PpM5VL) n and (PLA-PpM5VL) n
- FIG. 7 shows a representative example of size-exclusion chromatograms for a telechelic MVL, PLA-PMVL-PLA, and the corresponding (PMVL-PLA) n multiblock prepared using diacid chloride coupling approach.
- FIG. 8 shows a synthesis scheme of (PLLA-PpM5VL) n and (PLA-PpM5VL) n
- FIG. 9 shows a representative example of size-exclusion chromatograms for a telechelic
- FIG. 10 shows a representative examples of room temperature uniaxial extension of
- PLLA-PMVL-PLLA, PDLA-PMVL-PDLA, and PLA-PMVL-PLA triblocks are by adding a solution of lactide (either (+)/L lactide or (-)/L lactide) monomer to dihydroxy telechelic polyP-methyl-5-valerolactone in the presence of catalytic TBD.
- lactide either (+)/L lactide or (-)/L lactide
- the triblock synthesis can be accomplished in the melt or in toluene using Sn(oct) 2 as a catalyst. There is no evidence of significnat transesterification between the PMVL and PLA blocks when these conditions are used.
- the tacticity of the PLA blocks is contolled by changing the optical purity of the lactide monomer.
- the endblocks are atactic PLA.
- (+)-lactide or (-)-lactide is added the endblocks are, respectively, isotactic PDLA or PLLA.
- PLLA-PpM5VL-PLLA/PDLA- PPM5VL-PDLA stereocomplexes are easily prepared by blending PLLA-PMVL-PLLA and PDLA-PMVL-PDLA together. This is accomplished by dissoving both polymers in toluene. The solvent is slowly evaporated at room temperature to yield a film of the sterocomplex. This is proceedure is summarized in FIG. 11.
- FIG. 11 shows PLLA-PpM5VL-PLLA/PDLA-PpM5VL-PDLA sterocomplexes.
- FIGS. 12A-B show DSC thermograms for PLLA-PMVL-PLLA (A) and sc-PMVL-Psc
- FIGS. 13A-B show DMA isochronal temperature ramps for PLLA-PMVL-PLLA (A)
- FIG. 14 shows representative examples of room temperature uniaxial extension of
- PLA-PMVL-PLA (0.29) .93 ⁇ 0.6 9.1 ⁇ 1.1 90 ⁇ 130
- FIG. 15 shows synthesis of PMVL polyurethanes using methylene diphenyl diisocyanate
- FIG. 18 shows representative data for hysteresis test of PMVL polyurethane PMVL- PMDM2230 (0.4). The test is for 20 cycles of loading and unloading with crosshead
Abstract
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US9815808B2 (en) | 2016-02-29 | 2017-11-14 | Regents Of The University Of Minnesota | Recovery of monomer from polyurethane materials by depolymerization |
US10808084B2 (en) | 2016-09-23 | 2020-10-20 | Regents Of The University Of Minnesota | Methods for making renewable and chemically recyclable crosslinked polyester elastomers |
US11111206B2 (en) | 2017-09-20 | 2021-09-07 | Regents Of The University Of Minnesota | Monomers and polymers formed thereby |
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